Water-soluble organic compound of antimony and process of producing it



Patented Sept. 18, teas.

UNITED STATES PATENT OFFICE.

MORRIS S. KEABASCH, 0F COLLEGE PARK, MARYLAND, ASSIGNOR TO ELI LILLY AND COMPANY, OF INDIANAPOLIS, INDIANA, A CORPORATION OF INDIANA.

WATER-sonnet}; ORGANIC COMPOUND or ANTIMONY AND PROCESS or PRODUC- ING rr.

No Drawing.

- atom bonded by its remaining bond or bonds to a sulphur atom or atoms, and have each sulphur atom bonded to a carbon atom of an organic radical containing an acid group which has a free valence bond capable of being attached either to hydrogen or to a metal. While my invention contemplates that the first-named organic radical shall be either an aliphatic or ,an aromatic radical, yet I preferthat it be an aromatic radical, specifically a phenyl radical, and desirably that it be a substituted aromatic radical, and specifically a substituted phenyl radical in which one or. more of the hydrogen atoms of the phenyl group have been replaced by an amine group .or groups, and/or by a hydroxyl group or groups, and/or by a substituted amine or hydroxyl group or groups. The organic radical bonded to the sulphur may be either aliphatic or aromatic.

In the past, organic compounds of carbonbonded trivalent antimony have found no application as therapeutic agents, so far as I know, due to the fact that they are rela-. tively insoluble in water. Illustrations of such known organic compounds of trivalent r1de:

HN CO CH Application filed J'anuary 24, 1928. Serial No. 249,196.

(2) m-amino drochloride 01 st/ I oi phenyl stibinous chloride hycontaining sulfhydryl groups; including thioglycolic acid, fl-sulfhydryl butyric acid, thiomalic acid, thiosalicylic acid, sulfhydryl benzene sulfonic acid, mercapto benzothiazole carboxylic acid, and substitution products of i such acids, as well as other compounds containing'asul'thydryl (SH) group-or groups and an acidic group or groups such as the carboxylic group (-COOH) or the sulfonic group (-SO H). That patent, although in eluding claims covering generically certain water-soluble organo-anetallic compounds and the process of producing them when the metal M therein referred to has a valence greater than one, and although giving an antimony compound as one example of such generic type of compounds, was directed in itsmore specific claims to mercury compounds; and in addition, the antimony compound there disclosed was of pe'ntavalent antimony and not trivalent antimony; so that for'both reasons claims directed specifically to trivalent antimonycompounds could not be obtained therein. This present application, on the other hand, is directed specifically to-trivalent antimony compounds; and .the

more specific claims of the present applica tion are directed to substituted-aromatic trivalent-antimony thio-acid compounds, especially to substituted-phenyl trivalent-antimony-thio-aeid compounds, and their derivatives, and to the process of producing them.

This present invention permits the production of organic trivalent antimony compounds which are therapeutically active, which have a relatively small toxicity, and

which are quite readily soluble in water.

For instance, if the p-acetyl amino-phenyl stibinous chloride given under formula 1 above is treated, in a suitable solvent, with a thio-acid, such as thiosalicylic acid,.the following reaction takes place:

OOOH

This is a compound which is readily soluble sodium salt, which is soluble in Water. The

in sodium bicarbonatesolution, to form the reaction is obviously as follows:

coon

l HNCOCH:

4 5) Br-Sb=Y, in which R is any organic radical having a carbon atom directly attached by one bond to the antimony, and Y is a non-metallic divalent atom other than. of the sulphur family (in which family'I mean to include sulphur, selenium, and tellurium and these only) or two non-metallic monevalent atoms, such as members of the halogen family. The

organic radical which R represents may broadly be any organic radical of the aliphatic or aromatic series; but I prefer that it be an aromatic radical, such as the phenyl group,'and that this aromatic radical be a substituted aromaticradical, such'as a substituted phenyl group; and in most cases it ,o o oNa S o OONa 2H|O 2 CO1 HNCOCH:

seems better that Y be two atoms of chlorine, for instance, rather than a single atom of oxygen, because the chlorides are more soluble in organic re-agents than are the oxides.

For the thio acid used in theproccss, the a general formula is I-ISR H in which R as an aromatic or aliphatlc organlc radical having a carbon atom attached to the sulfhydryl group and also containing an acid group which has a free valence bond capable of being attached either to hydrogen to form the acid, as shown, or to a metal to form a salt of such acid. This wouldgive a final product containing a radical of the followmg typical formula:

In this final product, the antimony atom is directly bonded by one bond to a carbon atom of the radical R, and is directly bonded by two bonds to sulphur atoms; and each sulphur atom is directly bonded by one bond to a carbon atom of an organic radical which contains an acid group such as above defined;

so that such product, by the substitution of sodium or potassium for hydrogen at the free bondof the acid group, permits the preparation of a sodium or potassium salt soluble in Water.

those obtained from most other thio acids, in

1,684,920 Indeed, I prefer to use the sulfhydrytusually materially soluble in water, so that it 15 sulfonic acids as the thio acids. These have is necessary to produce salts thereof in order the advantage in that when they react with to get any material water solubility. In conthe initial trivalent antimony compound they sequence, by using sulfhydryl sulfonic acids, form acids which are themselves somewhat it is possible to get an aqueous solution of V water soluble, and which also can react with any desired hydrogen ion concentration with- 20 alkalis to form water-soluble salts. In this in a wide range extending on both sides of respect, the derivatives obtained from the the neutral point. sulfhydryl sulfonic acids are different from Thus, if instead of using thiosalicylic acid in the reaction shown in equation (3), one uses p-sult'hydryl benzene sulfonic acid, in- 25 stead of the reaction shown in equation (8), one would get the following reaction:

HNCOCH:

that with those other thio acids the acid formed by the'reaction of the initial trivalent-antimony compound with the initial thio acid produces acids which are themselves not HNCOOH:

nous iodide. The method is as follows :ten grams of p-hydroxy phenyl stibinic acid were dissolved in about 25 cc. concentrated hydrochloric acid (sp. gr. 1.18) and about 75 cc. glacial acetic acid, and filtered. A. crystal of iodine is added, and a solution of 15 grams stannous chloride in about cc. hydrochloric acid (sp. gr. 1.124) is added. Finally, thetheoretical amount of potassium iodide is added in a concentrated aqueous solution. It is best to'stand this soluction in the ice box'over night. The yellow crystalline precipitate is filtered ofl', washed with concentrated hydrochloric acid to remove tin compounds, then with ether, and dried. The crystals may be recrystallized from glacial acetic acid. Analysis indicated that the compound is probably of the structure indicated above. The compound has a melting point of 112115, and is rather insoluble in acetone, ether, and alcohol.

To 0.28 grams of p-hydroxy phenyl stibinous iodide, suspended in 20 cc. of methyl or ethyl alcohol, is added gradually with stirring an alcoholic solution of 0.18 grams thiosalicylic acid. The following reaction takes place:

The acid produced by the above reaction is somewhat water soluble; and the solution of it may be given varying hydrogen ion concentrations by the addition of varying amounts of an alkali.

The efiective compound thus produced thus contains a radical of the following general formula:

n'so.- R'so3' in which R may be a suitable organic radical combinable with the SO, group to form a sulfonic acid. The radical shown in Formula 8 is merely a more specific exampleot the radical shown in Formula 6. I give below a few examples of the many compounds which come within the scope of the broader claims of the present invention; though such examples are meant as illustrations and not as limitations.

Emample 1.

For this example, it was necessary to prepare. p-hydroxy phenyl stibinous iodide, HO'C I-L'Sb-I itself a new substance. This preparation was carried out in a manner analogous to the preparation of phenyl stibi-.

. v S I Sb I s COOH (j 2 HI. I H

COOH v I 7 /OOOH Q znsO H c I The solution is warmed on, the bath for residue, and concentrated to a small volume; p a short time at 50-60 (1, filtered from any It is allowed to drop into an equal volume of and ether, and moderately soluble in acetone, I

and slowly soluble in absolute alcohol.

It is soluble in dilute alkalies and dilute sodium bicarbonate solution. Upon acidifi l cationof the latter solution a precipitate forms which gives a good test for antimony. It formswater-soluble salts with the alkali metals such as sodium or potassium, with ammonia, and with the alkaline-earth metals such as calcium. The structural formula of the sodium salt is:

oooN s a .25 a 10 HOC SD O Y COONa It is obvious that instead of the phydrox phenyl stibinous iodide one may employ the corresponding chloride as the starting mate rial, Without affecting the final product.

Example 2.

' For this example, it was necessary to prepare p-hydroxy phenyl stibinous chloride, HOC H,-SbCl itself a new substance. This preparation was carried out in a manner 40 analogous to the method which may be used for the preparation of phenylstibinous chloride. The method is as follows: Ten grams of p-hydroxy phenyl stibinic acid were dissolved in about 25 c. c. concentrated hydro-'45 chloride (sp. gr. 1.18) and about 75 c. c. glacial acetic acid, and filtered. A crystal of iodine is added,'and a solution of 15 grams stannous chloride in about 40 c. c. hydrochloric acid (.sp. gr. 1.124) is added. It is best to stand this solution in the ice-box, say, over night. The yellow crystalline precipitate is filtered off, washed with a mixture of glacial acetic acid and concentrated hydrochloric acid, and pressed-out on a. porous plate. The analysis indicated that the compound-is probably of the structure indicated above. The compound has a melting point of about 128, and is insoluble in ether, benzene, and chloroform. Itis soluble in'ace-tone, methyland ethyl alcohol. v

. To a solution of 0.85 grams of p-hydroxy phenyl stibinous chloride in about 15 c. c. of methyl or. ethyl alcohol, is added gradually a solution of 1.1403 grams of p-sulihydryl benzene sulfonic acid, in about 35.0. c. of 95% alcohol. On'standing, a precipitate settles; out in accordance with'the reaction:

The precipitate which settles out in the tive test for antimony. The structural for Y above reaction is p-hydroxy phenylstibinous mulaof the sodium salt is:

p-sulfo-benzene sulfonic acid -having the structural formula of the first term on the right-hand side of the foregoing reaction equation.

This precipitate is collected on a filter, Washed with absolute alcohol, and dried. As ordinarily obtained by the above reaction,

this compound is a White substance which 30 does not melt or show signs of decomposition when heated to 300 C. It is quite readily soluble in water, concentrated hydrochloric acid, sodium carbonate, sodium bicarbonate, sodium hydroxide and 35 other alkali hydroxide solutions. It dissolves in sodium bicarbonate giving a solution chloride (for preparation, see

i s-O-smm 95.

SOSO:N& '(12) 1 Example 3.

To 0.283 grams p-hydroxy phen lstibinous xample 2) which, when faintly acidified throws out the dissolved in about 30 c. c. of either methyl or acid again, and this acid gives a good qu'alitaethyl alcohol, is added with stirring an alcoholic solution of 0.2 grams of thioglycolic acid. The reaction mixture may be warmed The product of the reaction, p-hydroxy phenylstibinous thioglycolic acid, having the structural formula of the first term on the right-hand side of the foregoing reaction equation, is isolated by evaporation of the solvent until a curdy residue remains, at which point other is added and the insoluble portion collected on a filter, Washed with ether and dried.

5 to minutes on'the bath at-5060 C. The following reaction takes place:

" soH,co011 soroooon 21101 The product is very soluble in methyl alcohol, moderately soluble in acetone, and insoluble in ether and concentrated hydrochloric acid. It decomposes in a'melting point tube. It is soluble in dilute alkali solution, and precipitates out as a fiocculent material, when the alkaline solution is acidi-' fied. The water-soluble sodium salt has the structural formula:

(1'4) O somooo1va SOHzGOONa EmampZe 4.

To 0.4 grams p-acetyl amino phenyl stibinous chloride hydrochloride monohydrate in about 15 c. c. ethyl alcohol is added an alcoholic solution of 0.34 grams thiosalicylic acid. The mixture is warmed to 60 0., and held 0 Sb 0 incl-H10 o O OH NHCOOHH The product of the reaction has the formula of the first term on the right-hand side of the foregoing reaction equation. This precipitate is collected on a filter, washed well with water, and dried on a porous plate in a desiccator, and may be used Without separating any unchanged reactants which may be present. The product is a white substance, melt ing around 200 G. It is-soluble in alcohol,

NHOOCHa ExompZa 5.

I To 0.95 grams of p-ace'tyl amino phenylstibinous chloride hydrochloride monohydrate,

l .o s

at that temperature about five minutes. The

solution is then filtered, and poured into an equal volume of water. The precipitate which separates is the p-acetyl amino phenyl stibinous thiosalicylic acid, with any unchanged reactants, obtained by the following NHoooH dilute sodium hydroxide and sodium bicarbonate solutions. ltdissolves readily in 1% sodium bicarbonate giving a solution which when acidified throws out the material again,

and this material gives a good qualitative test for antimony.

The sodium, potassium, ammonium, and calcium salts are soluble in water. The water-solublesodium salt has the formula:

GOONa 0 ONE dissolvedin a small volume of ethyl or methyl I alcohol is added gradually with stirrin an alcoholic solution of 0.66 grams of B-su thydryl propionic acid. The reaction mixture may takes place:

NHOOCHI The product of the reaction, p-acetyl amino phenyl stibinous sulfo-propionic acid, having the structural formula of the firstterm on the righthand side of the foregoing reac- 2 HS GHICHICOOHfl be warmed on bath at 50-00 to complete reaction. The following reaction b SCHr CHzCOOH scHr cmcoon NHCOCH:

tled out, which crystallized on standing. The material is filtered ofi', Washed with ether and dried. It shrinks at 100102 C. and melts at 105-107 C. It is slightly soluble in water, readily soluble in dilute alkalies,for1ning soluble salts, the structure of the sodium salt being:

OHIOHiOOONB NHCOCH:

Ewample 6. To 0.90 grams phenyl stibinous iodide, dissolved in asmall quantity of ethyl or methyl alcohol, is added gradually with stirring an The precipitate, the phenyl stibinous sulfobenzene-sulfonic acid, having the structural formula as indicated in the first termon the I right-hand side of the foregoing reaction equation, is filtered off, washedthoroug'hly with absolute alcohol, and dried on porous plate in a desiccator.

The phenyl stibinous sulfo-benzene sulfonic acid is of a pale cream color, and does not melt or darken when heated to 300 C.

The precipitate which is p-acteyl amino phenyl stibinous sulfo-benzene sulfonic acid,

having the structural formula as indicated in the first term on the'right-hand side of the (19) znsOsouL O alcoholic solution containing 0.76 grams of 20 p-sulfhydryl benzene sulfonlc acid. A white precipitate forms during the addition of the sulfonic acid, indicating that the following reaction has taken place:

nous chloride. hydrochloride monohydrate, dissolved in about 25 c. c. of ethyl or methyl alcohol, is added gradually with stirring, an alcoholic solution containing 1.90 grams of p-sulfhydryl benzene sulfonic acid. -A light colored precipitate forms immediately during the addition of the sulphonic acid, indicating-that the following reaction has taken place. .45

. s O/ SHCI 1110 NHOOCH:

foregoing reaction equation, is filtered 011', .50 washedwith absolute alcohol, and dried on a clay plate in a desiccator.

The p-acetyl amino phenyl stibinous sulfo I benzene sulphonicacid is a light brown crystalline substance which does not melt or darken when heated to 300 C. i It is somewhat soluble in water. It forms water-soluble salts with the alkali metals "such as sodium and potassium, with ammonia, and with the alkaline earth metals such as calcium. The structural formula of the sodium salt is:

SOa Na solution of the sodium salt of p-acetyl amina phenyl stibinous sulfo-henzene -sulphonic acid shows a marked trypanocidal activity.

Emample8,

For this example, it was necessary to prepare p-amino phenyl stibinous chloride which, so far as is known, is undescribed in the literature. The method is essentially as follows: p-amino phenyl stibinic acid in moist condi- The precipitate, the hydrochloride of p-amino phenyl stibinous sulfo-loenzene sulfonic acid, having the structural formula as indicated in the first termon the right-hand side of the foregoing reaction equation, is filtered off, washedwith absolute alcohol, and dried on a porous plate in a desiccator.

The hydrochloride of p-ainino phenyl stihinous sulfo-benzene sulfonic acid is of a palecream color, andv did not melt or darken when heatedto 300 C. It is somewhat soluble in;

water and alcohol, and forms water-soluble salts with the alkali metals such as sodium or potassium, with ammonia, and with the alkaline earth metals such as calcium. The structural formula of the sodium salt is s-Osonm S- SOaNa o1 v /OOOH uni-n01 tion (4 grams calculated on dry basis) and 10 rams stannous chloride'were treated gradsis of the compound agreed most. closely with In a melting point tube, it shrinks at 120 C, darkens at I the formula, NH -C H -SbCl 220C., and is not melted at 270 C.'

To 1.0248 grams of p-amino phenyl stihinous chloride, suspended in c. 0. methyl or. ethyl alcohol, is addedgradually 1.1403 grams of p-sulfhydryl benzene sulfonic acid, dissolved inthe minimum amount of. methyl or ethyl alcohols, and the solution warmed on the steam bath for one hour. Filtered, and

allowed to cool. A precipitate settled out,

indicating that the following reaction had taken place N-i1o1 Example 9.

To 0.30 grams of p-amino chloride hydrochloride,

phenyl stibinous suspended in. a small quantity of alcohol or.

acetone, is added graduallywith stirring a concentrated alcoholic solution of 0.30 gram of thiosalicylie acid,

The whole goes into solution, the following reaction taking place: I Y

.ooon 2K" COOH The alcohol solution, if not completely clear, is filtered, and the filtrate dropped into water.

The p-amino phenylstibinous thiosalicylic acid hydrochloride, having the structural formula of the first term on the right hand side of the foregoing reaction equation separates out, and may be filtered off, dissolved in sodium carbonate, and is reprecipitated by acid ifying, when 'a white flocculent precipitate rem sults. This precipitate is filtered and dried.

When air dried, it begins to decompose around 110; The material is rather insoluble in acetone and alcohol, but dissolves very readily when hydrochloric acid is added to the solvent.

It is soluble in solutions of sodium bicarbonate, sodium carbonate, and alkali hydroxides, and slightly soluble in calcium hydroxide solutions.

' sodium salt is:

COONa i 45 CO0Ne The structural formula of the It isnot necessary to start with the hydrochloride of p-amino phenyl 'stibinous chloride, since the p-amino phenyl s'tibinous chloride or the p-amino phenyl stibinous oxide works just as well.

Example 10.

The hydrochloride of meta amino phenyl 4 0 stibinous chloride may be condensed with thiosalicylic acid, following the procedure outlined in Exampleil for the para derivative, and the meta product thus obtained is similar in all respects to the para product above described.

Ewaxr np le To isolate the product thus obtained two methods may be employed. Either the alcohol can be taken off in vacuo at a low temperature, or the condensation product may be:

precipitated with ether. In either case a white substance 1s obtained which is exceed- '65 ingly hygroscopic, and for that reason it is difficult to determine the decomposition point of this material. The productthus obtained is readily soluble in hydrochloric acid (due to the presence of the amino group in the mole- Instead of the iodide, one of course may emcule), aswell as in alkalies such as sodium and potassium hydroxide and alkali carbonates. It is also soluble in ammonium hydroxide.

E i-ample 12. 85 Phenyl stibinous iodide (one mole), which is rather insoluble in alcohol, is treated with two moles of thio salicylic acid, whereupon the whole material goes into solution very readily, the following reaction taklng place:

COOH

COOH

chloride. The condensation product thus ploy more advantageously the oxide or the obtained is isolated by pouring the aeoholic solution into water. A white precipitate of phenyl stibinous thio-sa-licylic acid'isobtained, which is soluble in sodium carbonate but insoluble in hydrochloric or sulfuric acids. The melting point is 186.

I claim as my. invention:

1. The step in the method of producing water -soluble compounds of organic stibinous compounds, which comprises treating, in a solvent, a stibinous compound in which at least one valence bond of the antimony is attached to an inorganic radical of other than solvent, a stibinous compound in which at least one valence bond of the antimony is attached to an inorganic radical of other than the sulphur family (sulphur, selenium, and

tellurium) and at least one valence bond of the antimony is directly attached to a carbon atom of an organic radical of the aromatic series, with an organic compound containing both an acid radical and a sulfhydryl group and having the sulfhydryl group directly attached to a carbon atom.

3. The step in the method of producing water-soluble compounds of organic stibinous compounds, which comprises treating, in a solvent, a stibinous compound in which at least one valence bond of the antimony is attached to an inorganic radical of other than the sulphur family (sulphur, selenium,

and tellurium) and at least one valence bond of the antimony is directly attached to a'carbon atom of a substituted aromatic radical, with an organic compound eontaining'both an acid radical and a sulfhydryl group and having the sulfhydryl group directly attached to a carbon atom.

4. The step in the method of producing water-soluble compounds of organic stibinous compounds, which comprises treating, in a solvent, 21 stibinous compound in which at least onevalence bond of the antimony is attached to an inorganic radical of other than the sulphur family (sulphur, selenium, and tellurium) and at least one valence bond of the antimony is directly attached to a carbon atom of a substituted phenyl radical, with an organic compound containing both an acid radical and a sulfhydryl group and having the sulfhydryl group. directly at tached to a carbon atom.

5. The step in the method of producing water-soluble compounds of organicstibinous compounds, which comprises treating,

in a solvent, a compound of the formula R- Sb=Y, in which Y comprises one or morp replaceable inorganic radicals or groups other than of the sulphur family (sulphur, selenium, and tellurium) and having a total valence of two, and in which R is an organic radical having a carbonatom to which the antimony is directly attached, with an organic compound containing both an acid radical and a sulfhydryl group and having the sulfhydryl group directly attached to a carbon atom.

6. The step in the method of producing water-soluble compounds of organic stibinous compounds, which comprises treating, in asolvent, a compound of the formula RSb=Y, in which Y comprises one or more replaceable inorganic radicals or groups other than of the sulphur family (sulphur, selenium, and tellurium) and having .a total valence of two, and in which R is a substituted aromatic radical having a carbon atom to which the antimony is directly attached, with an organic compound containing both an acid radical and a sulfhydryl group and having the sulfhydryl group directly attached to a carbon atom.

water-soluble compounds of organic stibinous compounds, which comprises treating, in a solvent, a compound of the formula RSb=O, in which R is an organic radical having a carbon atom to which the antimony is directly attached, with an organic compound containing both an acid radical and a sulfhydryl group and havingthe sulfhydryl group directly attached to a carbon atom. v

- 8. The step in the method of producing water-soluble compounds of organic stibi-' nous compounds, which comprises treating, in a solvent, a compound of the formula RSb=O, in which R is a substituted aromatic radical having a carbon atom to which the antimony is directly attached, with an organic compound containing both an acid radical and a sulfhydryl group and having the sulfhydryl group directly attached to a carbon atom.

7. The step inthe method of producing 9. A stibinous organic compound, in which at least one bond of a trivalent-antimony valence bond capable of being attached either to hydrogen or to a metal.

10. A stibinous organic compound, in which at least one bond of a trivalent-antimony atom is attached to a carbon atom of an aromatic radical, and at least one other bond of the trivalent-antimony atom is attached to a sulphur atom, and the sulphur is also attached to a carbon atom of an organic radical containing an acid group which has a free valence bond capable of being attached either to hydrogen or to a metal.

11. A stibinous organic compound, in which at least one bond of a trivalent-antimony atom isattached to a carbon atom of a substituted aromatic radical, andat least one other bond of the trivalent-antimony atom is attached to a sulphur atom, and the sulphur is also attached to a carbon atom of an organic radical containing, an acid group which has a free valence bond capable of'being attached either to hydrogen or to a metal.

12. A stibinous organic compound, in

which at least one bond of a trivalent-anti-- .lnony atom is attached to a carbon atom of a substituted phenyl radical, and at least one other bond of the trivalent-antimony atom is attached to a sulphur atom, and the sulphur is also attached to a carbon atom of an OI'OADIC radical containing an acid group A w 1ich has a free valence bond capable of being attached either to hydrogen or to a metal. -l3. A compound containing the following radical:

where R is any organic radical having a carbon atom directly attached to the antimony, and R is an organic radical having a carbon 7 atom directly attached to the sulphur atom and containing. an acid group which has a free valence bond capable of being attached either to hydrogen or to a metal.

14. A compound containing the following radical:

s'RAu R s RAo where R is an aromatic radical having a carbon atom directly attached to the antimony, and R is an organic radical having a. carbon atom directly attached to the sulphur atom and contain ng an acid group Which has a free valence bond capable of being attached either to hydrogen or to a metal.

15. A compound containing the following radicalz- S-RA S RAcv where R is a substituted aromatic radical having a carbon atom directly attached to the antimony, and R is an organic radical having a carbon atom directly attached to the sulphur atom and containing an acid group i which has a free valence bond capable of being attached either to hydrogen or to a metal. 16. A compound containing the following radical:

where R is a substituted phenyl radical have ing a carbon atom directly attached to the antimony, and R is an organic radical having a carbon atom directly attached to the sulphur atom and containing an acid group which has a free valence bond capable of being attached either to hydrogen or to a metal.- 17. A compound containing the following radical:

R Sb SRSO:

where R is any organic radical having a carbon atom directly attached to the antimony, and R is an organic radical which has a carbon atom directly attached to the sulfide sulphur atom and which is combinable with an SO group to form a sulfonic acid. 18. A compound containing the following radical: 8

where R is an aromatic radical having a carbon atom directly attached to the antimony,

and R is an organic radical which has a car- 00 bon atom directly attached .to the sulfide sulphur atom and which is combinable with an SO group to form a sulfonic acid.-

19. A compound containing the following radical Where R is ,a substituted aromatic radical having a carbon atom directly attached to the antimony, and R. is an organic radical which has a carbon atom directly-attached to the sulfide sulphur atom and which is combinable with an S0, group to form a sulfonic acid.

20. A compound containing the following radical: U

where R is a substituted phenyl radical having a carbon atom directly attached to the antimony, and R is an organic radical which has a carbon atom directly attached to the sulfide sulphur atom and which is combinable with an SO group to form a sulfonic acid. 21. A compound containing 'thefollowing radical: l

in which R is an aromatic radical having a 130 carbon atom niony. Q Y

- 23. A comp radical:

directly attached to the antiound containing the following in which R is a'substituted phenyl radical having a carbon atom directly'attached to the 20 antimony.

In witness whereof, I have hereunto set my hand at Indianapolis, Indiana, this 28th day in which R is a substituted aromaticiradical of December, A. I). one thousand nine hun having a carbon atom directly attached to dred and twenty seven.

the antimony.

' MORRIS S. KHARASOH. 

